Substrate processing method

ABSTRACT

A substrate processing method includes a substrate holding step of holding a substrate horizontally, a liquid droplet discharging step wherein liquid droplets of an organic solvent, formed by mixing the organic solvent and a gas, are discharged from a double-fluid nozzle toward a predetermined discharge region within an upper surface of the substrate, and a liquid film forming step, executed before the liquid droplet discharging step, of supplying the organic solvent to the double fluid nozzle without supplying the gas, so as to discharge the organic solvent in a continuous stream mode from the double-fluid nozzle to form a liquid film of the organic solvent covering the discharge region on the upper surface of the substrate.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. patent application Ser. No.14/978,693, filed Dec. 22, 2015, which claims the benefit of JapanesePatent Application No. 2014-265537, filed Dec. 26, 2014, the contents ofwhich are incorporated herein by reference.

BACKGROUND OF THE INVENTION 1. Field of the Invention

The present invention relates to a substrate processing method forprocessing a substrate by using an organic solvent. Examples ofsubstrates to be processed include semiconductor wafers, substrates forliquid crystal displays, substrates for plasma displays, substrates forFEDs (Field Emission Displays), substrates for optical disks, substratesfor magnetic disks, substrates for magneto-optical disks, substrates forphotomasks, ceramic substrates, substrates for solar cells, etc.

2. Description of Related Art

In a manufacturing process for a semiconductor device or a liquidcrystal display, a cleaning processing of supplying a cleaning liquid toa major surface of substrate, such as a semiconductor wafer or a glasssubstrate for liquid crystal display panel, etc., to clean the majorsurface of the substrate with the cleaning liquid is performed. Forexample, a substrate processing apparatus of a single substrateprocessing type that processes a substrate at a time includes a spinchuck that rotates the substrate while holding the substratesubstantially horizontally by means of a plurality of chuck pins and anozzle arranged to supply a cleaning liquid to a major surface of thesubstrate rotated by the spin chuck.

In the arrangement of U.S. Patent Application No. 2003/178047 A1, aspouting nozzle that spouts minute liquid droplets of the cleaningliquid is used as the nozzle instead of a straight nozzle thatdischarges a continuous stream. Also, isopropyl alcohol (IPA) is used asthe cleaning liquid. That is, with the arrangement of U.S. PatentApplication No. 2003/178047 A1, minute liquid droplets of IPA that arespouted from the spouting nozzle are supplied to the major surface ofthe substrate and the major surface is cleaned thereby.

SUMMARY OF THE INVENTION

However, at the start of discharge of the organic solvent (IPA) liquiddroplets, a particle diameter distribution of the organic solvent liquiddroplets discharged from a double-fluid nozzle (spouting nozzle) is inan unstable state. Therefore, when the discharge of the organic solventliquid droplets from the double-fluid nozzle onto an upper surface(major surface) of the substrate is started, the organic solvent liquiddroplets in the state of unstable particle diameter distribution collidedirectly against the upper surface of the substrate that is in a drystate and this may cause particles to form on the upper surface of thesubstrate.

An object of the present invention is thus to provide a substrateprocessing method by which a substrate can be processed satisfactorilyusing liquid droplets of an organic solvent from a double-fluid nozzlewhile suppressing formation of particles.

The present invention provides a substrate processing method including asubstrate holding step of holding a substrate horizontally, a liquiddroplet discharging step of making liquid droplets of an organicsolvent, formed by mixing the organic solvent and a gas, be dischargedfrom a double-fluid nozzle toward a predetermined discharge regionwithin an upper surface of the substrate, and a liquid film formingstep, executed before the liquid droplet discharging step, of supplyingthe organic solvent to the double fluid nozzle without supplying the gasto discharge the organic solvent in a continuous stream mode from thedouble-fluid nozzle to form a liquid film of the organic solventcovering the discharge region.

With the present method, the organic solvent liquid droplets aredischarged from the double-fluid nozzle toward the discharge regionwithin the upper surface of the substrate. Foreign matter (particles,etc.) attached to the discharge region are removed physically bycollision of the organic solvent liquid droplets against the uppersurface of the substrate. The upper surface of the substrate can therebybe processed satisfactorily.

Also, the organic solvent liquid film that covers the discharge regionis formed on the upper surface of the substrate before the discharge ofthe organic solvent liquid droplets. Therefore, the organic solventliquid droplets discharged from the double-fluid nozzle collide againstthe organic solvent liquid film covering the discharge region. Theorganic solvent liquid droplets can thus be prevented from directlycolliding against the upper surface of the substrate in a dry state atthe start of liquid droplet discharge at which a particle diameterdistribution of the discharged organic solvent liquid droplets isunstable. Formation of particles in accompaniment with the execution ofthe liquid droplet discharging step can thus be suppressed.

Also, the organic solvent discharged from the double-fluid nozzle can beswitched from the continuous stream mode to a liquid droplet mode byswitching the supplying of the gas to the double-fluid nozzle from astopped state to a supplying state. The organic solvent used in theliquid droplet discharging step and the organic solvent used in theliquid film forming step are discharged from a nozzle in common andtherefore the liquid droplet discharging step can be started withoutdelay after stopping the supplying of the organic solvent in the liquidfilm forming step. That is, the organic solvent can be supplied withoutinterruption to the upper surface of the substrate. Drying of the uppersurface of the substrate during transition from the liquid film formingstep to the liquid droplet discharging step can thus be suppressed andformation of particles can thus be suppressed effectively during thetransition from the liquid film forming step to the liquid dropletdischarging step.

By the above, the substrate can be processed satisfactorily using theorganic solvent liquid droplets from a double-fluid nozzle whilesuppressing the formation of particles.

Also, the substrate processing method may further include a firstrotating step of rotating the substrate around the rotational axis inparallel to the liquid droplet discharging step.

With the present method, the organic solvent liquid film is formed onthe upper surface of the substrate in the liquid droplet dischargingstep. The substrate is rotated in parallel to the liquid dropletdischarging step and therefore the liquid film formed on the uppersurface of the substrate can be made thin. The organic solvent liquiddroplets can thus be made to arrive on the upper surface of thesubstrate and foreign matter attached to the upper surface of thesubstrate can thus be removed satisfactorily.

Also, the substrate processing method may further include apost-supplying step of supplying the organic solvent to the uppersurface of the substrate after the liquid droplet discharging step.

With the present method, the organic solvent is supplied to the uppersurface of the substrate in the post-supplying step performed after theliquid droplet discharging step. The foreign matter removed from thesubstrate upper surface by the physical cleaning in the liquid dropletdischarging step can thus be rinsed off by the organic solvent andreattachment of the foreign matter onto the upper surface of thesubstrate can thereby be suppressed or prevented.

Also, the substrate processing method may further include a secondrotating step, executed in parallel to the post-supplying step, ofrotating the substrate around the rotational axis at a higher speed thanthat in the first rotating step.

With the present method, the rotation speed of the substrate in thepost-supplying step is higher than that in the first rotating step andtherefore a large centrifugal force acts on the organic solvent suppliedto the upper surface of the substrate. The foreign matter removed fromthe substrate upper surface by the physical cleaning can thereby be spunoff from sides of the substrate together with the organic solvent andremaining of the foreign matter on the upper surface of the substratecan thus be suppressed or prevented.

Also, with the substrate processing method, in the post-supplying step,the organic solvent may be supplied to the double-fluid nozzle withoutsupplying the gas to discharge the organic solvent in a continuousstream mode from the double-fluid nozzle.

With the present method, the organic solvent discharged from thedouble-fluid nozzle can be switched from the liquid droplet mode to thecontinuous stream mode by switching the supplying of the gas to thedouble-fluid nozzle from the supplying state to the stopped state. Theorganic solvent used in the liquid droplet discharging step and theorganic solvent used in the post-supplying step are discharged from anozzle in common and therefore the post-supplying step can be startedwithout delay after stopping the supplying of the organic solvent in theliquid droplet discharging step. That is, the organic solvent can besupplied without interruption to the upper surface of the substrate.Drying of the upper surface of the substrate during transition from theliquid droplet discharging step to the post-supplying step can thus besuppressed and formation of particles can thus be suppressed effectivelyduring the transition from the liquid droplet discharging step to thepost-supplying step.

The substrate treatment method may further include a nozzle moving stepof moving the double fluid nozzle, and the liquid droplet dischargingstep may start discharging of droplets of the organic solvent to alanded position of the organic solvent on the upper surface of thesubstrate at the end of the liquid film forming step, as the dischargeregion.

In this case, the discharge region can be reliably covered with theorganic solvent liquid film at the start of discharge of droplets of theorganic solvent. Therefore, direct collision of droplets of the organicsolvent against the upper surface of the substrate in the dry state canbe reliably avoided at the start of discharge of droplets of the organicsolvent, even in case of forming the liquid film while moving thedouble-fluid nozzle.

The landed position may include a peripheral edge on the upper surfaceof the substrate, and the liquid droplet discharging step startsdischarging of droplets of the organic solvent to the peripheral edge onthe upper surface of the substrate, as the discharge region.

Also, the liquid droplet discharging step may be a step that is executedin a state where a first guard is made to face a peripheral end surfaceof the substrate, and the substrate processing method may furtherinclude a drying step of rotating the substrate around the rotationalaxis, without supplying the organic solvent to the upper surface of thesubstrate, to dry the upper surface of the substrate and a facing guardchanging step of changing the guard facing the peripheral end surface ofthe substrate from the first guard to a second guard, differing from thefirst guard, after the liquid droplet discharging step is ended andbefore the drying step is executed.

With the present method, in the liquid droplet discharging step in whichthe upper surface of the substrate is physically cleaned by the organicsolvent liquid droplets, the organic solvent expelled from the substratemay contain foreign matter removed from the substrate. During the liquiddroplet discharging step, the first guard faces the peripheral endsurface of the substrate and the organic solvent that contains foreignmatter may thus be attached to the first guard.

However, during the drying step, the second guard is made to face theperipheral end surface of the substrate instead of the first guard thatmay have the foreign-matter-containing organic solvent attached thereto.Therefore during the drying step, the substrate after the cleaningprocessing can be suppressed effectively from being contaminated by theorganic solvent (foreign-matter-containing organic solvent) attached tothe guard facing the peripheral end surface of the substrate.

Also, the substrate processing method may further include a dischargeregion moving step of moving the position of the discharge region withinthe upper surface of the substrate and an additional organic solventsupplying step of supplying, in parallel to the discharge region movingstep, the organic solvent to a rearward position with respect to adirection of progress of the discharge region. In this case, the organicsolvent does not have to be supplied to a forward position with respectto the direction of progress of the discharge region in the additionalorganic solvent supplying step.

With the present method, regardless of where in the upper surface of thesubstrate the position of the discharge region is disposed, the organicsolvent is supplied separately to a vicinity of the position of thedischarge region. Although if the upper surface of the substrate driesduring the liquid droplet discharging step, particles may form in thedried region, with the present method, the organic solvent is suppliedto the vicinity of the position of the discharge region and thereforedrying of the upper surface of the substrate during the liquid dropletdischarging step can be prevented.

If, for instance, the organic solvent is supplied to a forward positionwith respect to the direction of progress of the discharge region of theorganic solvent liquid droplets from the double-fluid nozzle, theorganic solvent liquid film at the discharge region becomes thick. Ifthe liquid film that covers the discharge region is thick, the organicsolvent may splash in accompaniment with the discharge of the organicsolvent liquid droplets onto the discharge region. Contaminantscontained in the organic solvent may scatter to the periphery due to thesplashing of the organic solvent and may cause particle formation.

With the present method, the organic solvent is supplied only to therearward position with respect to the direction of progress of thedischarge region and therefore the organic solvent liquid film at thedischarge region can be kept thin while preventing the drying of theupper surface of the substrate. Splashing of the organic solventdischarged onto the discharge region can thus be suppressed. Formationof particles in accompaniment with the execution of the liquid dropletdischarging step can thereby be suppressed more effectively.

Also, the substrate processing method may further include a firstpreliminary preparation step of preparing a silicon substrate, havingSiO₂ disposed at the upper surface, as the substrate.

With the present method, the organic solvent is low in etching powerwith respect to SiO₂. Therefore, a surface of the silicon substrate canbe cleaned satisfactorily without excessively etching the SiO₂ disposedat the upper surface of the substrate.

Also, the substrate processing method may further include a secondpreliminary preparation step of preparing a semiconductor substrate,including an insulating film constituted of a low dielectric constantmaterial of lower relative dielectric constant than SiO₂ and a copperwiring disposed on the insulating film, as the substrate.

With the present method, the organic solvent is used as the cleaningliquid to clean the upper surface of the substrate. The organic solventis low in oxidizing power with respect to copper. The upper surface ofthe semiconductor substrate can thus be cleaned satisfactorily withoutexcessively etching the copper wiring.

In this case, the organic solvent may have a low surface tension. A lowdielectric constant material has a high contact angle and therefore asurface of the insulating film exhibits high hydrophobicity(lyophobicity). However, the surface of the insulating film having highhydrophobicity can be wetted satisfactorily by using an organic solvent,having a low surface tension, as the cleaning liquid. A liquid film ofthe organic solvent that covers an entirety of the upper surface of thesemiconductor substrate can thereby be formed satisfactorily.

The above and yet other objects, features, and effects of the presentinvention shall be made clear by the following description of thepreferred embodiments in reference to the attached drawings.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a diagram of a substrate processing apparatus which executes asubstrate processing method according to a first preferred embodiment ofthe present invention as viewed from a horizontal direction.

FIG. 2A is an illustrative sectional view of the arrangement of adouble-fluid nozzle included in the substrate processing apparatus.

FIG. 2B is a block diagram for explaining the electrical structure ofthe substrate treatment apparatus shown in FIG. 1.

FIG. 3 is an enlarged sectional view of a vicinity of a front surface ofa substrate to be processed by the substrate processing apparatus.

FIGS. 4A to 4C are illustrative sectional views showing a method formanufacturing the substrate shown in FIG. 3 in order of process.

FIG. 5 is a flowchart for describing a processing example of a cleaningprocessing performed by the substrate processing apparatus.

FIGS. 6A and 6B are illustrative diagrams for describing the processingexample of the cleaning processing.

FIGS. 6C and 6D are schematic diagrams for describing processesfollowing that of FIG. 6B.

FIG. 6E is a schematic diagram for describing a process following thatof FIG. 6D.

FIGS. 7A and 7B are diagrams of test results of a first cleaning testperformed with an example.

FIG. 8 is a diagram of a test result of the first cleaning testperformed with a comparative example.

FIG. 9 is a schematic plan view for describing a particle mode.

FIG. 10 is a diagram of test results of a second cleaning test.

FIG. 11 is an illustrative diagram of a portion of a substrateprocessing apparatus which executes a substrate processing methodaccording to a second preferred embodiment of the present invention.

FIGS. 12A and 12B are illustrative diagrams for describing a processingexample of a cleaning processing according to the second preferredembodiment of the present invention.

FIG. 13 is an enlarged sectional view of a vicinity of a front surfaceof another substrate to be processed.

FIGS. 14A to 14C are illustrative sectional views showing a method formanufacturing the substrate shown in FIG. 13 in order of process.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS

FIG. 1 is a diagram of a substrate processing apparatus 1 which executesa substrate processing method according to a first preferred embodimentof the present invention as viewed from a horizontal direction. FIG. 2Ais an illustrative sectional view of the arrangement of a double-fluidnozzle 16 included in the substrate processing apparatus 1.

The substrate processing apparatus 1 is a single substrate processingtype apparatus arranged to perform a cleaning processing on a majorsurface (upper surface) at a device formation region side of a substrateW, such as a silicon substrate 61 (see FIG. 3). The substrate processingapparatus 1 includes a box-shaped processing chamber 2 having aninternal space, a spin chuck (substrate holding unit) 3 holding a singlesubstrate W in a horizontal attitude inside the processing chamber 2 androtating the substrate W around a vertical rotational axis A1 passingthrough the center of the substrate W, a double-fluid nozzle 16 arrangedto discharge liquid droplets of IPA that is an example of an organicsolvent onto an upper surface of the substrate W held by the spin chuck3, an organic solvent supplying unit (first organic solvent supplyingunit) 4 arranged to supply IPA to the double-fluid nozzle 16, a gassupplying unit (gas supplying unit) 80 arranged to supply nitrogen gasas an example of a gas to the double-fluid nozzle 16, a cylindricalprocessing cup 5 surrounding the spin chuck 3, and a controller (controlunit) 7 controlling operations of apparatuses and opening/closing ofvalves provided in the substrate processing apparatus 1.

The processing chamber 2 includes a box-shaped partition wall 8, an FFU(fan filter unit) 9 as a blower unit delivering clean air from an upperportion of the partition wall 8 into an interior of the partition wall 8(corresponding to an interior of the processing chamber 2), and anexhaust apparatus 10 expelling gas inside the processing chamber 2 froma lower portion of the partition wall 8. The spin chuck 3 and thedouble-fluid nozzle 16 are housed and disposed within the partition wall8.

The FFU 9 is disposed above the partition wall 8 and is mounted on aroof of the partition wall 8. The FFU 9 delivers the clean air into theprocessing chamber 6 from the roof of the partition wall 13. The exhaustapparatus 10 is connected via an exhaust duct 11, connected to aninterior of the processing cup 5, to a bottom portion of the processingcup 5 and suctions the interior of the processing cup 5 from the bottomportion of the processing cup 5. A down flow (downward flow) is formedinside the processing chamber 6 by the FFU 9 and the exhaust apparatus10.

As the spin chuck 3, a clamping type chuck, which clamps the substrate Win horizontal directions to hold the substrate W horizontally, isadopted. Specifically, the spin chuck 3 includes a spin motor (substraterotating unit) 12, a spin shaft 13 made integral to a drive shaft of thespin motor 12, and a disk-shaped spin base 14 mounted substantiallyhorizontally on an upper end of the spin shaft 13.

A plurality (not less than three, that is, for example, six) of clampingmembers 15 are disposed at a peripheral edge portion of an upper surfaceof the spin base 14. At the upper surface peripheral edge portion of thespin base 14, the plurality of clamping members 15 are disposed atsuitable intervals on a circumference corresponding to an outerperipheral shape of the substrate W.

Also, the spin chuck 3 is not restricted to a clamping type and, forexample, a vacuum suction type arrangement (vacuum chuck) thatvacuum-suctions a rear surface of the substrate W to hold the substrateW in a horizontal attitude and further performs rotation around avertical rotation axis in this state to rotate the substrate W held bythe spin chuck 3 may be adopted instead.

The double-fluid nozzle 16 has a basic form of a scan nozzle capable ofchanging a position on a front surface of the substrate W to which IPAis supplied (discharge region D1 (see FIG. 6B)). The double-fluid nozzle16 is mounted to a tip portion of a nozzle arm 17 extendingsubstantially horizontally above the spin chuck 3. The nozzle arm 17 issupported by an arm supporting shaft 18 extending substantiallyvertically at a side of the spin chuck 3. An arm swinging unit (nozzlemoving unit) 19 is coupled to the arm supporting shaft 18. Thedouble-fluid nozzle 16 is arranged to be capable of being moved abovethe spin chuck 3 between the rotational axis A1 of the substrate W and aperipheral edge of the substrate W by swinging the nozzle arm 17 byturning the arm supporting shaft 18 by a driving force of the armswinging unit 19. It is also made capable of being moved from above thespin chuck 3 toward a home position at a side of the spin chuck 3.

The organic solvent supplying unit 4 includes an organic solvent piping20 supplying liquid IPA at ordinary temperature from an IPA supplysource to the double-fluid nozzle 16, an organic solvent valve 21switching between supplying and stopping the supply of IPA from theorganic solvent piping 20 to the double-fluid nozzle 16, and a flowcontrol valve 22 adjusting an opening degree of the organic solventpiping 20 to adjust a flow rate of IPA discharged from the double-fluidnozzle 16. As shall be described later, the IPA discharged from thedouble-fluid nozzle 16 is used not only in an IPA liquid dropletdischarging step (S4 of FIG. 5) but also in an IPA liquid film formingstep (S3 of FIG. 5) and an IPA post-supplying step (S5 of FIG. 5). Thatis, second and third organic solvent supplying units are realized by theorganic solvent supplying unit 4 and the double-fluid nozzle 16.

A gas supplying unit 80 includes a first gas piping 23 supplying a gasfrom a gas supply source and a first gas valve 24 switching betweensupplying and stopping the supply of gas from the first gas piping 23 tothe double-fluid nozzle 16. As the gas supplied to the double-fluidnozzle 16, an inert gas, dry air, or clean air, etc., maybe used besidesnitrogen gas.

As shown in FIG. 2A, the double-fluid nozzle 16 has a substantiallycircular columnar outer shape. The double-fluid nozzle 16 includes anouter cylinder 26 constituting a casing and an inner cylinder 27 fittedin an interior of the outer cylinder 26.

The outer cylinder 26 and the inner cylinder 27 are respectivelydisposed coaxially on a central axis L in common and are joined to eachother. An internal space of the inner cylinder 27 is a rectilinearorganic solvent flow passage 28 through which the IPA from the organicsolvent piping 20 flows. Also, a circular cylindrical first gas flowpassage 29, through which the gas supplied from the first gas piping 23flows, is formed between the outer cylinder 26 and the inner cylinder27.

The organic solvent flow passage 28 opens as an organic solvent inlet 30at an upper end of the inner cylinder 27. The IPA from the organicsolvent piping 20 is introduced via the organic solvent inlet 30 intothe organic solvent flow passage 28. Also, the organic solvent flowpassage 28 opens as a circular organic solvent discharge port 31 havinga center on the central axis L at a lower end of the inner cylinder 27.The IPA introduced into the organic solvent flow passage 28 isdischarged from the organic solvent discharge port 31.

On the other hand, the first gas flow passage 29 is a circularcylindrical gap having a central axis in common with the central axis L,is closed at upper end portions of the outer cylinder 26 and the innercylinder 27, and opens as a circular annular gas discharge port 32,having a center on the central axis L and surrounding the organicsolvent discharge port 31, at lower ends of the outer cylinder 26 andthe inner cylinder 27. A lower end portion of the first gas flow passage29 is made smaller in flow passage area than an intermediate portion ina length direction of the first gas flow passage 29 and decreases indiameter toward a lower side. Also, a gas inlet 33 in communication withthe first gas flow passage 29 is defined at an intermediate portion ofthe outer cylinder 26.

The first gas piping 23 is connected in a state of penetrating throughthe outer cylinder 26 to the gas inlet 33 and an internal space of thefirst gas piping 23 is in communication with the first gas flow passage29. The gas from the first gas piping 23 is introduced via the gas inlet33 into the first gas flow passage 29 and is discharged from the gasdischarge port 32.

By opening the organic solvent valve 21 to make the IPA be dischargedfrom the organic solvent discharge port 31 while opening the first gasvalve 24 to make the gas be discharged from the gas discharge port 32,the gas can be made to collide (mix) with the IPA at a vicinity of thedouble-fluid nozzle 16 to thereby form minute liquid droplets of the IPAand discharge the IPA in the form of a mist.

On the other hand, by opening the organic solvent valve 21 to make theIPA be discharged from the organic solvent discharge port 31 with thefirst gas valve 24 being closed, the IPA can be discharged from thedouble-fluid nozzle 16 in a continuous stream mode. Hereinafter, the IPA(organic solvent) in the continuous stream mode shall be referred to asthe “continuous stream of IPA (organic solvent).”

As shown in FIG. 1, the processing cup 5 includes a cylindrical wall 35surrounding the spin chuck 3 and having, for example, a circularcylindrical shape, a plurality of cups 36 and 37 (first and second cups36 and 37) disposed fixedly between the spin chuck 3 and the cylindricalwall 35, a plurality of guards 38 and 39 (first and second guards 38 and39) arranged to receive the IPA that is scattered to a periphery of thesubstrate W, and a guard raising/lowering unit (guard raising/loweringunit) 40 that raises and lowers each of the guards 38 and 39independently. The processing cup 5 is collapsible.

The cylindrical wall 35 surrounds a periphery of the spin chuck 3. Thecylindrical wall 35 is arranged to be capable of storing IPA in itsinterior. The IPA stored in the cylindrical wall 35 is guided to a drainequipment (not shown). Also, an upstream end of an exhaust duct 11 isconnected to a predetermined location in a circumferential direction ofa lower end portion of the cylindrical wall 35. The atmosphere insidethe cylindrical wall 35 is exhausted through the exhaust duct 11 by theexhaust apparatus 10.

Each of the cups 36 and 37 defines an upwardly-open, annular groove. TheIPA guided to the first cup 36 is delivered through a first piping (notshown) connected to a bottom portion of the groove to a recoveryequipment (not shown) or the drain equipment (not shown). The IPA guidedto the second cup 37 is delivered through a second piping (not shown)connected to a bottom portion of the groove to the recovery equipment(not shown) or the drain equipment (not shown). The IPA used inprocessing the substrate W is thereby subject to a recovery processingor a drain processing.

Each of the guards 38 and 39 has a circular cylindrical incliningportion 41 extending obliquely upward toward the rotational axis A1 anda circular cylindrical guide portion 42 extending downward from a bottomend of the inclining portion 41. An upper end portion of each incliningportion 41 constitutes an inner peripheral portion of the guard 38 or 39and has a larger diameter than the substrate W and the spin base 14. Thetwo inclining portions 41 are overlapped vertically and the two guideportions 42 are disposed coaxially. Each of the guide portions 42 of theguards 38 and 39 is capable of entering into and exiting from thecorresponding cup 36 or 37. The processing cup 5 is extended orcollapsed by the guard raising/lowering unit 40 raising or lowering atleast one of the two guards 38 and 39. In FIG. 1, a state in which theprocessing cup 5 differs at the right side and the left side of therotational axis A1 is illustrated for the sake of description.

The guard raising/lowering unit 40 raises and lowers each of the guards38 and 39 between an upper position, at which an upper end of the guardis positioned higher than the substrate W, and a lower position, atwhich the upper end of the guard is positioned lower than the substrateW. The guard raising/lowering unit 40 is capable of holding each of theguards 38 and 39 at any position between the upper position and thelower position. The supplying of IPA to the substrate W and the dryingof the substrate W are performed in a state where either of the guards38 and 39 faces a peripheral end surface of the substrate W. Forexample, if the first guard 38 at the inner side is to be made to facethe peripheral end surface of the substrate W, the guards 38 and 39 aredisposed at the lower position (state shown at the right side in FIG.1). Also, if the second guard 39 is to be made to face the peripheralend surface of the substrate W, the first guard 38 is disposed at thelower position and the second guard 39 is disposed at the upper position(state shown at the left side in FIG. 1).

As shown in FIG. 1, the substrate processing apparatus 1 furtherincludes a gas discharge nozzle 6 arranged to perform gas dischargeabove the substrate W held by the spin chuck 3. The gas discharge nozzle6 includes an annular upper gas discharge port 44 opening outward at anouter peripheral surface that is a side surface of the gas dischargenozzle 6, an annular lower gas discharge port 45 opening outward at theouter peripheral surface that is the side surface of the gas dischargenozzle 6, and a central gas discharge port 46 opening downward at alower surface of the gas discharge nozzle 6. The upper gas dischargeport 44 is disposed higher than the lower gas discharge port 45. Thecentral gas discharge port 46 is disposed lower than the upper gasdischarge port 44 and the lower gas discharge port 45 and further inward(further toward a central axis A2 of the gas discharge nozzle 6) thanthe upper gas discharge port 44 and the lower gas discharge port 45. Theupper gas discharge port 44 and the lower gas discharge port 45 areslit-shaped discharge ports centered at the central axis A2 of the gasdischarge nozzle 6 and surrounding an entire circumference of the sidesurface of the gas discharge nozzle 6. An outer diameter of the uppergas discharge port 44 may be equal to an outer diameter of the lower gasdischarge port 45 or may be greater or less than the outer diameter ofthe lower gas discharge port 45.

The gas discharge nozzle 6 is a circular columnar member of smallerdiameter than the substrate W. A second gas piping 48 and a third gaspiping 49 are connected to the gas discharge nozzle 6. Second and thirdgas valves 50 and 51 are respectively interposed in the second and thirdgas pipings 48 and 49. The gas from the gas supply source is introducedinto the gas discharge nozzle 6 via the second gas piping 48 and issupplied to the upper gas discharge port 44 and the lower gas dischargeport 45 via a second gas flow passage (not shown). Also, the gas flowinginside the third gas piping 49 is introduced into the gas dischargenozzle 6 via the third gas piping 49 and is supplied to the central gasdischarge port 46 via a third gas flow passage (not shown). When thesecond gas valve 50 is opened, the gas is discharged radially to aperiphery of the gas discharge nozzle 6 from the gas discharge ports 44and 45. When the third gas valve 51 is opened, the gas is dischargeddownward from the central gas discharge port 46. Although nitrogen gasis indicated as an example of the gas supplied to the gas dischargenozzle 6, an inert gas, dry air, or clean air, etc., may be used insteadas the gas.

A gas nozzle moving unit 52 is coupled to the gas discharge nozzle 6.The gas nozzle moving unit 52 makes the gas discharge nozzle 6 turnaround a vertical swinging axis (not shown) provided at a side of thespin chuck 3. The gas nozzle moving unit 52 also moves the gas dischargenozzle 6 in an up/down direction. When the gas nozzle moving unit 52raises or lowers the gas discharge nozzle 6 when the gas dischargenozzle 6 is positioned above the substrate W, the gas discharge nozzle 6is raised or lowered above the substrate W so that a distance betweenthe substrate W and the gas discharge nozzle 6 changes. The gas nozzlemoving unit 52 also makes the gas discharge nozzle 6, be positioned, forexample, at any of a retracted position, an upper position (the positionshown in FIG. 1), and a proximity position (position shown in FIG. 6E).The retracted position is a position at which the gas discharge nozzle 6is retracted to a side of the spin chuck 3 and the upper position andthe proximity position are positions at which the gas discharge nozzle 6is positioned above a central portion of the substrate W. The upperposition is a position above the proximity position and the proximityposition is a position at which the lower surface of the gas dischargenozzle 6 is made more proximal to an upper surface central portion ofthe substrate W than at the upper position. The gas nozzle moving unit52 is capable of holding the gas discharge nozzle 6 at any positionbetween the retracted position and the upper position and any positionbetween the upper position and the proximity position.

FIG. 2B is a block diagram for explaining the electrical structure ofthe substrate treatment apparatus 1. The controller 7 has an arrangementthat includes a microcomputer. The controller 7 includes an operationunit including a CPU and the like, a storage unit comprising a read-onlymemory device, and an input-output unit. A program for the operationunit executes is stored in the storage unit.

The controller 7 is connected to the operations of the exhaust apparatus10, the spin motor 12, the arm swinging unit 19, the guardraising/lowering unit 40, the gas nozzle moving unit 52, the organicsolvent valve 21, the flow control valve 22, the first gas valve 24, andthe like. The controller 7 controls the operations of the exhaustapparatus 10, the spin motor 12, the arm swinging unit 19, the guardraising/lowering unit 40, the gas nozzle moving unit 52, etc., inaccordance with a predetermined program. The controller 7 controls theopening and closing operation etc. on the organic solvent valve 21, theflow control valve 22, the first gas valve 24, etc., in accordance witha predetermined program.

FIG. 3 is an enlarged sectional view of a vicinity of the front surfaceof the substrate W to be processed by the substrate processing apparatus1.

The substrate W to be processed constitutes a base of a MOSFET andincludes the silicon substrate 61. At a surface layer portion of thesilicon substrate 61, trenches 62 are formed by digging from the frontsurface. A plurality of the trenches 62 are formed at fixed intervals ina right/left direction in FIG. 3 with each extending in a directionorthogonal to a paper surface of FIG. 3. SiO₂ 63 (silicon oxide) isembedded in each trench 62. The SiO₂ 63 forms element separatingportions 64 that insulate element forming regions from other regions.The element separating portion 64 has an STI structure, with which thetrench 62 is refilled with an insulating material (SiO₂ 63). A frontsurface of the SiO₂ 63 is made substantially flush with the frontsurface of the silicon substrate 61.

FIGS. 4A to 4C are illustrative sectional views showing a method formanufacturing the substrate W in order of process. As shown in FIG. 4A,first, the trenches 62 are formed by reactive ion etching in the surfacelayer portion of the silicon substrate 61. Next, an SiO₂ film 65 isformed by a vacuum CVD (chemical vapor deposition) method on an uppersurface of the silicon substrate W and inside each trench 62 as shown inFIG. 4B. As shown in FIG. 4B, the SiO₂ film 65 fills the interiors ofthe trenches 62 completely and is also formed on the silicon substrate61 outside the trenches 62.

Next, portions of the SiO₂ film 65 protruding outside the respectivetrenches 62 are removed selectively by a CMP (chemical mechanicalpolishing) method. A front surface of the SiO₂ film 65 is thereby made aflat surface that is substantially flush with the front surface of thesilicon substrate 61 and the element separating portions 64 are formedas shown in FIG. 4C (first preliminary preparation step).

The element separating portions 64 are formed by polishing the SiO₂ film65 by the CMP method and therefore particles 66, such as SiO₂ polishingscraps (slurry), etc., are present on the surface layer portion of thesubstrate W immediately after manufacture. The substrate processingapparatus 1 applies the cleaning processing to the substrate W to removethe SiO₂ polishing scraps and other particles 66 from the substrate W.

In such a cleaning processing, the use of SC1 (ammonia-hydrogen peroxidemixture) as a cleaning liquid may be considered. However, when SC1 isused to clean the front surface of the substrate W, the elementseparating portions 64 that are constituted of SiO₂ may become etchedexcessively and the front surfaces of the element separating portions 64may become recessed. In this case, not only are the element separatingcharacteristics of the element separating portions 64 degraded but theMOSFET may also become poor in flatness after manufacture of the MOSFET.

On the other hand, in the cleaning processing according to the presentpreferred embodiment, the front surface (upper surface) of the substrateW is cleaned using IPA as the cleaning liquid. IPA has only low etchingpower with respect to SiO₂. The front surface (upper surface) of thesubstrate W can thus be cleaned satisfactorily without excessivelyetching the element separating portions 64 that are constituted of SiO₂.

FIG. 5 is a flowchart for describing a processing example of thecleaning processing performed by the substrate processing apparatus 1.FIGS. 6A to 6E are illustrative diagrams for describing the processingexample of the cleaning processing.

An example of the cleaning processing shall now be described withreference to FIG. 1, FIG. 3, and FIG. 5. FIGS. 6A to 6E shall bereferenced where appropriate.

When the cleaning processing is to be applied to the substrate W by thesubstrate processing apparatus 1, the substrate W (in the state shown inFIG. 4C) after removal of the SiO₂ film 65 (see FIG. 4B) by CMP iscarried into the interior of the processing chamber 2 (step S1 of FIG.5). Specifically, the controller 7 makes a hand (not shown) of asubstrate transfer robot (not shown), which holds the substrate W, enterinto the interior of the processing chamber 2 in a state where allnozzles are retracted from above the spin chuck 3 and the first andsecond guards 38 are lowered to the lower position so that the upperends of the first and second guards 38 and 39 are all disposed lowerthan the position of holding of the substrate W by the spin chuck 3. Thesubstrate W is thereby passed onto the spin chuck 3 and held by the spinchuck 3 in a state where the major surface, which is to be processed, isfaced upward (substrate holding step).

Thereafter, the controller 7 controls the guard raising/lowering unit 40to raise both the first and second guards 38 and 39 to the upperpositions and make the first guard 38 face the peripheral end surface ofthe substrate W.

The controller 7 starts the rotation of the substrate W by the spinmotor 12 (step S2 of FIG. 5). The rotation speed of the substrate W israised to a predetermined first high rotation speed (for example ofapproximately 1000 rpm) and is held at that first high rotation speed.

When rotation of the substrate W reaches the first high rotation speed,the controller 7 then performs the IPA liquid film forming step (liquidfilm forming step; step S3 of FIG. 5) of forming a liquid film of IPA onthe upper surface of the substrate W as shown in FIG. 6A. Specifically,the controller 7 controls the arm swinging unit 19 so that thedouble-fluid nozzle 16 is moved from the home position retracted to theside of the spin chuck 3 to a central position (position indicated bysolid lines in FIG. 6A), at which the discharged IPA lands on an uppersurface central portion of the substrate W, and then kept still at thecentral position. After the double-fluid nozzle 16 is disposed at thecentral position, the controller 7 opens the organic solvent valve 21while closing the first gas valve 24. A continuous stream of IPA isthereby discharged from the double-fluid nozzle 16. The discharge flowrate of the IPA from the double-fluid nozzle 16 is set to a low flowrate (for example of 0.1 (liters/minute)) by opening degree adjustmentof the organic solvent piping 20 by the flow control valve 22. Also, aperiod from the start of rotation of the substrate W to the start ofdischarge of the IPA is, for example, approximately 2.5 seconds.

As shown in FIG. 6A, the IPA discharged from the double-fluid nozzle 16lands on the upper surface of the substrate W rotating at the first highrotation speed and thereafter receives a centrifugal force due to therotation of the substrate W and flows outward along the upper surface ofthe substrate W. The IPA is thus supplied to an entirety of the uppersurface of the substrate W and an IPA liquid film covering the entiretyof the upper surface of the substrate W is formed on the substrate W.The IPA that has reached a peripheral edge portion upon flowing on theupper surface of the substrate W is scattered toward sides of thesubstrate W from the peripheral edge portion of the substrate W.

As shown in FIG. 6A, the IPA that scatters from the peripheral edgeportion of the substrate W is received by an inner wall of the firstguard 38. The IPA that flows down along the inner wall of the firstguard 38 is received by the first cup 36 and collected at a bottomportion of the first cup 36. The IPA collected at the bottom portion ofthe first cup 36 is delivered through the first piping (not shown) tothe recovery equipment (not shown) or the drain equipment (not shown).

When a predetermined period elapses from the start of discharge of theIPA, the controller 7 controls the spin motor 12 to decelerate therotation speed of the substrate W to a liquid processing speed (forexample of approximately 400 rpm) and maintain the rotation speed at theliquid processing speed. Thereafter, while sustaining the discharge ofIPA from the double-fluid nozzle 16 (while maintaining the dischargeflow rate of IPA as it is), the controller 7 controls the arm swingingunit 19 so that the double-fluid nozzle 16 is moved toward a peripheraledge position (position indicated by solid lines in FIG. 6B), at whichthe IPA discharged from the double-fluid nozzle 16 lands on an uppersurface peripheral edge portion of the substrate W, and disposed at theperipheral edge position. The IPA liquid film forming step (S3) isthereby ended. A processing period of the IPA liquid film forming step(S3) is, for example, approximately 5 to 6 seconds.

Also, the rotation speed of the substrate W is decelerated to the liquidprocessing speed prior to the end of the IPA liquid film forming step(S3) because if the rotation of the substrate W at the first highrotation speed is continued as it is, the IPA supplied to the uppersurface of the substrate W may volatilize, causing the upper surface ofthe substrate W to dry and thereby cause particle formation.

After the double-fluid nozzle 16 is disposed at the peripheral edgeposition, the IPA liquid droplet discharging step (liquid dropletdischarging step; first rotating step; step S4 of FIG. 5) of dischargingliquid droplets of the IPA onto the upper surface of the substrate Wfrom the double-fluid nozzle 16 is performed as shown in FIG. 6B.Specifically, the controller 7 opens the first gas valve 24 whilesustaining the discharge of IPA (while maintaining the discharge flowrate of IPA as it is). The IPA and the nitrogen gas, which is an exampleof the gas, are thereby supplied simultaneously to the double-fluidnozzle 16 and the supplied IPA and nitrogen gas are mixed at a vicinityof the discharge port (organic solvent discharge port 31 (see FIG. 2B))at the exterior of the double-fluid nozzle 16. A jet of minute liquiddroplets of the IPA is thereby formed and the jet of IPA liquid dropletsis discharged from the double-fluid nozzle 16. A circular dischargeregion D1 is thus formed on the upper surface of the substrate W and theposition of the discharge region D1 is disposed at a peripheral edgeportion of the substrate W.

Numerous IPA liquid droplets from the double-fluid nozzle 16 are blownonto the discharge region D1 of the substrate W and therefore foreignmatter (particles, etc.) attached to the discharge region D1 can beremoved physically by collision of the IPA liquid droplets (physicalcleaning). Also, the IPA liquid droplets are blown onto the dischargeregion D1 in the state where the entirety of the upper surface of thesubstrate W is covered by the liquid film and thereafter reattachment ofthe foreign matter to the substrate W is suppressed or prevented.

Also, the IPA liquid film covering the discharge region D1 is formed onthe upper surface of the substrate W prior to the discharge of the IPAliquid droplets. Therefore, at the start of discharge of the IPA liquiddroplets, the IPA liquid droplets discharged from the double-fluidnozzle 16 collide against the IPA liquid film covering the dischargeregion D1. Direct collision of the IPA liquid droplets against the uppersurface of the substrate Win the dry state can thus be avoided at thestart of discharge of the IPA liquid droplets.

Also, by switching the supplying of the gas to the double-fluid nozzle16 from the stopped state to the supplying state while sustaining thesupplying of the IPA to the double-fluid nozzle 16, the IPA dischargedfrom the double-fluid nozzle 16 can be switched from the continuousstream mode to the liquid droplet mode. That is, the IPA supplied to theupper surface of the substrate W in the IPA liquid film forming step(S3) is discharged from the double-fluid nozzle 16.

Also, in parallel to the discharge of the jet of IPA liquid dropletsfrom the double-fluid nozzle 16, the controller 7 controls the armswinging unit 19 to make the double-fluid nozzle 16 move back and forthhorizontally between the central position and the peripheral edgeposition. Specifically, first, the double-fluid nozzle 16 disposed atthe peripheral edge position is moved toward the central position. Theposition of the discharge region D1 is thereby moved along the uppersurface of the substrate W toward the central axis A1 while beingcovered by the IPA liquid film.

When the double-fluid nozzle 16 reaches the central position, thecontroller 7 controls the arm swinging unit 19 to reverse the swingingdirection of the nozzle arm 17. The double-fluid nozzle 16 is thus madeto start movement from the central position toward the peripheral edgeposition. The position of the discharge region D1 is thereby moved alongthe upper surface of the substrate W toward the peripheral edge portionof the substrate W while being covered by the IPA liquid film. When thedouble-fluid nozzle 16 reaches the peripheral edge position, thecontroller 7 controls the arm swinging unit 19 to reverse the swingingdirection of the nozzle arm 17. The position of the discharge region D1is thereby moved along the upper surface of the substrate W toward thecentral axis A1. The position of the discharge region D1 is thus movedback and forth between the peripheral edge portion of the substrate Wand the central portion of the substrate W.

The double-fluid nozzle 16 is moved between the central position and theperipheral edge position while rotating the substrate W, and thereforethe upper surface of the substrate W is scanned by the discharge regionD1 and the position of the discharge region D1 passes through theentirety of the upper surface of the substrate W. The IPA dischargedfrom the double-fluid nozzle 16 is thus supplied to the entirety of theupper surface of the substrate W and the entirety of the upper surfaceof the substrate W is processed uniformly. The IPA supplied to the uppersurface of the substrate W is scattered from the peripheral edge portionof the substrate W toward the sides of the substrate W.

A moving speed of the double-fluid nozzle 16 (that is, a scanning speedof the discharge region D1) is set, for example, to approximately 30 to80 mm/second.

As shown in FIG. 6B, the IPA that scatters from the peripheral edgeportion of the substrate W is received by the inner wall of the firstguard 38. The IPA that flows down along the inner wall of the firstguard 38 is received by the first cup 36 and collected at the bottomportion of the first cup 36. The IPA collected at the bottom portion ofthe first cup 36 is delivered through the first piping (not shown) tothe recovery equipment (not shown) or the drain equipment (not shown).

When a predetermined period elapses from the start of supply of gas withrespect to the double-fluid nozzle 16, the controller 7 controls thespin motor 12 to accelerate the rotation speed of the substrate W to asecond high rotation speed (for example of approximately 1000 rpm) andthereafter maintain the rotation speed at the second high rotationspeed. Also, while sustaining the discharge of IPA, the controller 7controls the arm swinging unit 19 so that the double-fluid nozzle 16 ismoved toward the central position and disposed at the central position.The IPA liquid droplet discharging step (S4) is thereby ended. Aprocessing period of the IPA liquid droplet discharging step (S4) is,for example, approximately 8 to 96 seconds.

After the double-fluid nozzle 16 is disposed at the central position, anIPA post-supplying step (post-supplying step; second rotating step; stepS5 of FIG. 5) of supplying a continuous stream of IPA to the uppersurface of the substrate W is performed as shown in FIG. 6C.Specifically, the controller 7 closes the first gas valve 24 that wasopen up to this point. The supplying of the gas with respect to thedouble-fluid nozzle 16 is thereby stopped and the continuous stream ofIPA is discharged from the double-fluid nozzle 16 (the discharge flowrate of IPA is 0.1 (liters/minute)). By switching the supplying of thegas to the double-fluid nozzle 16 from the supplying state to thestopped state while sustaining the supplying of the IPA to thedouble-fluid nozzle 16, the IPA discharged from the double-fluid nozzlecan be switched from the liquid droplet mode to the continuous streammode.

The continuous stream of IPA discharged from the double-fluid nozzle 16lands on the upper surface of the substrate W rotating at the secondhigh rotation speed and thereafter receives a centrifugal force due tothe rotation of the substrate W and flows outward along the uppersurface of the substrate W. The IPA is thus supplied to the entirety ofthe upper surface of the substrate W and an IPA liquid film covering theentirety of the upper surface of the substrate W is formed on thesubstrate W as shown in FIG. 6C. The IPA that has reached the peripheraledge portion upon flowing on the upper surface of the substrate W isscattered toward the sides of the substrate W from the peripheral edgeportion of the substrate W. In the IPA post-supplying step (S5), theforeign matter removed from the substrate W upper surface by thephysical cleaning in the IPA liquid droplet discharging step (S4) isrinsed off by the IPA.

Also, the IPA liquid film formed on the upper surface of the substrate Wcan be levelled prior to a drying step (S7) because the IPA liquid filmis formed on the upper surface of the substrate Win the IPApost-supplying step (S5).

As shown in FIG. 6C, the IPA that scatters from the peripheral edgeportion of the substrate W is received by the inner wall of the firstguard 38. The IPA that flows down along the inner wall of the firstguard 38 is received by the first cup 36 and collected at the bottomportion of the first cup 36. The IPA collected at the bottom portion ofthe first cup 36 is delivered through the first piping (not shown) tothe recovery equipment (not shown) or the drain equipment (not shown).

When a predetermined period elapses from the start of discharge of theIPA, the controller 7 controls the spin motor 12 to decelerate therotation speed of the substrate W to a medium rotation speed (forexample of approximately 500 rpm) and maintain the rotation speed at themedium rotation speed. Thereafter, the controller 7 controls the organicsolvent valve 21 to stop the discharge of IPA from the double-fluidnozzle 16 and controls the arm swinging unit 19 so that the double-fluidnozzle 16 is retracted from the central position (processing position)to the home position. The IPA post-supplying step (S5) is ended bystoppage of discharge of IPA from the double-fluid nozzle 16. Aprocessing period of the IPA post-supplying step (S5) is, for example,approximately 5 to 6 seconds.

Also, the rotation speed of the substrate W is decelerated to the mediumrotation speed prior to the end of the IPA post-supplying step (S5)because if the rotation of the substrate W at the second high rotationspeed is continued as it is, the IPA supplied to the upper surface ofthe substrate W may volatilize, causing the upper surface of thesubstrate W to dry and thereby cause particle formation.

After the discharge of IPA from the double-fluid nozzle 16 is stopped,the controller 7 controls the spin motor 12 to decelerate the rotationspeed of the substrate W, rotating at the medium rotation speed, to alow rotation speed (for example of approximately 10 rpm) and maintainthe rotation speed at the low rotation speed. The low rotation speed maybe zero (that is, stoppage of rotation).

After the substrate W reaches the low rotation speed, the controller 7controls the guard raising/lowering unit 40, while maintaining therotation speed of the substrate W at the low rotation speed, to lowerthe first guard 38 from the upper position to the lower position whilemaintaining the second guard 39 at the upper position and thereby makethe second guard 39 face the peripheral end surface of the substrate Was shown in FIG. 6D. That is, the guard facing the peripheral endsurface of the substrate W is switched (changed (step S6 of FIG. 5:facing guard changing step)) from the first guard 38 to the second guard39.

After the second guard 39 is disposed to face the peripheral end surfaceof the substrate W, the controller 7 executes the drying step (step S7of FIG. 5) as shown in FIG. 6E.

Specifically, the controller 7 controls the spin motor 12 to increasethe rotation speed of the substrate W from the low rotation speed. Also,the controller 7 controls the gas nozzle moving unit 52 to move the gasdischarge nozzle 6 from the upper position to the proximity position.After the gas discharge nozzle 6 is disposed at the proximity position,the controller 7 opens the second gas valve 50 and the third gas valve51 to make nitrogen gas, which is an example of the gas, be dischargedfrom the three gas discharge ports (the upper gas discharge port 44, thelower gas discharge port 45, and the central gas discharge port 46).Three annular gas streams overlapping in the up/down direction arethereby formed above the substrate W and the upper surface of thesubstrate W is protected by the three annular gas streams.

After starting the discharge of nitrogen gas from the three gasdischarge ports 44, 45, and 46 of the gas discharge nozzle 6, thecontroller 7 controls the spin motor 12 to make the substrate W rotateat a predetermined drying speed (for example of approximately 1000 rpm).The IPA on the substrate W is thereby spun off outward and the substrateW dries. Also, the drying of the substrate W is performed in a statewhere the upper surface of the substrate W is covered by the threeannular gas streams, and therefore particles and other foreign matterand IPA mist that are suspended inside the processing chamber 2 aresuppressed or prevented from attaching to the substrate W during thedrying step (S7).

The IPA liquid droplets that scatter from the peripheral edge portion ofthe substrate W in the drying step (S7) are received by an inner wall ofthe second guard 39 as shown in FIG. 6E. The IPA that flows down alongthe inner wall of the second guard 39 is received by the second cup 37and collected at a bottom portion of the second cup 37. The IPAcollected at the bottom portion of the second cup 37 is deliveredthrough the second piping (not shown) to the recovery equipment (notshown) or the drain equipment (not shown).

When the drying step (S7) has been performed for a predetermined period(for example of 12 seconds), the controller 7 drives the spin motor 12to stop the rotation of the spin chuck 3 (rotation of the substrate W)(step S8 of FIG. 5). After stopping the rotation of the substrate W bythe spin chuck 3, the controller 7 closes the second gas valve 50 andthe third gas valve 51 to stop the discharge of gas from the three gasdischarge ports 44, 45, and 46. After stopping the discharge of gas fromthe three gas discharge ports 44, 45, and 46, the controller 7 controlsthe gas nozzle moving unit 52 to make the gas discharge nozzle 6 retractto the periphery of the spin chuck 3.

The cleaning processing of the single substrate W is thereby ended and,as when the substrate W was carried in, the controller 7 carries theprocessed substrate W out from inside the processing chamber 2 by meansof the transfer robot (step S9 of FIG. 5).

First and second cleaning tests shall now be described.

In each of the first and second cleaning tests, a substrate processingmethod (cleaning processing) according to an example described below isapplied to a sample.

Example: A bare silicon substrate W (outer diameter: 300 (mm)) wasadopted as the sample and IPA was adopted as the organic solvent. Thesubstrate processing apparatus 1 was used to execute the processingexample of the cleaning processing shown in FIG. 5 to FIG. 6E describedabove on the sample held by the spin chuck 3 (see FIG. 1) and put in arotating state.

Also, in the first cleaning test, a substrate processing method(cleaning processing) according to a comparative example described belowis applied to a sample.

Comparative example: A bare silicon substrate W (outer diameter: 300(mm)) was adopted as the sample and IPA was adopted as the organicsolvent. The substrate processing apparatus 1 was used to execute acleaning processing on the sample held by the spin chuck 3 (see FIG. 1)and put in a rotating state. The cleaning processing according to thecomparative example differs from the processing example of the cleaningprocessing shown in FIG. 5, FIG. 6B, FIG. 6D, and FIG. 6E describedabove in the point that both the IPA liquid film forming step (S3 ofFIG. 5) and the IPA post-supplying step (S5 of FIG. 5) are abolished andis the same as the processing example of the cleaning processingdescribed above in regard to other points.

<First Cleaning Test>

For the example, a distribution and number of particles on the frontsurface of the substrate W after the cleaning processing were measured.The cleaning test was performed twice and test results of the firstcleaning test performed with the example are shown respectively in FIGS.7A and 7B.

On the front surface of the substrate W after the cleaning test shown inFIG. 7A, 47 particles of not less than 26 nm were present. The number ofparticles on the front surface of the substrate W before performing thetest was 46 and although this means that the number of particlesincreased by one, this is within the range of measurement error. It istherefore believed that there is no practical increase or decrease inthe number of particles on the substrate W front surface before andafter the cleaning test.

Also, on the front surface of the substrate W after the cleaning testshown in FIG. 7B, 32 particles of not less than 26 nm were present. Thenumber of particles on the front surface of the substrate W beforeperforming the cleaning test was 25 and although this means that thenumber of particles increased by seven, this is within the range ofmeasurement error. It is therefore believed that there is no practicalincrease or decrease in the number of particles on the substrate W frontsurface before and after the cleaning test.

It can thus be understood that when both the IPA liquid film formingstep (S3 of FIG. 5) and the IPA post-supplying step (S5 of FIG. 5) areperformed, particles formed in the IPA liquid droplet discharging step(S4 of FIG. 5) can be suppressed effectively from remaining on thesubstrate W.

Meanwhile, for the comparative example, the distribution and number ofparticles on the front surface of the substrate W after the cleaningprocessing were measured. A test result of the first cleaning testperformed with a comparative example is shown in FIG. 8. A measurementresult of the particle distribution is shown in FIG. 8. White portionsappearing in FIG. 8 are particles. On the front surface of the substrateW after the cleaning test, not less than approximately 45000 particleswere present. It can thus be understood that when both the IPA liquidfilm forming step (S3 of FIG. 5) and the IPA post-supplying step (S5 ofFIG. 5) are not performed, many of the particles formed in the IPAliquid droplet discharging step (S4 of FIG. 5) remain on the frontsurface of the substrate W.

A description regarding the distribution of particles shall now beprovided. In each of the examples of FIG. 7A and FIG. 7B, biasing of theparticles on the substrate W after the cleaning test was not seen inparticular. On the other hand, with the comparative example of FIG. 8, apattern where especially many particles form in a double annular form atthe peripheral edge portion of the substrate W was seen. A reason forformation of the particle pattern at the peripheral edge portion of thesubstrate W is considered to be that the IPA liquid film forming step(S3 of FIG. 5) was not performed before the IPA liquid dropletdischarging step (S4 of FIG. 5). That is, in the IPA liquid dropletdischarging step (S4 of FIG. 5), the double-fluid nozzle 16 startsscanning the substrate W from the peripheral edge portion of thesubstrate W. The IPA liquid droplets from the double-fluid nozzle 16immediately after the start of discharge vary greatly in particlediameter. It is known that particle characteristics of the substrate Wafter cleaning degrade when the jet of IPA liquid droplets, which varygreatly in particle diameter, is made to collide against the substrate Wfront surface. In each of the examples of FIG. 7A and FIG. 7B, the IPAliquid film forming step (S3 of FIG. 5) is performed before the IPAliquid droplet discharging step (S4 of FIG. 5) and therefore the jet ofIPA liquid droplets collide not directly against the front surface ofthe substrate W but collide via the IPA liquid film. The particlecharacteristics at the peripheral edge portion of the substrate W (thatis, at the location at which the jet of IPA liquid droplets is orientedimmediately after the start of discharge) are thus satisfactory. On theother hand, with the comparative example of FIG. 8, the IPA liquid filmforming step (S3 of FIG. 5) is not performed and the jet of IPA liquiddroplets, which vary greatly in particle diameter, collide against thefront surface of the substrate W without intervention of an IPA liquidfilm. The particle characteristics are thus degraded at the peripheraledge portion of the substrate W.

Further, a reason as to why the mode of particles exhibit a doubleannular form at the peripheral edge portion of the substrate W in FIG. 8is considered to be as follows. That is, in the circular dischargeregion D1 (see FIG. 6B) on the upper surface of the substrate W, whereasa large amount of liquid droplets are supplied to a central portion ofthe discharge region D1, only a minute amount of liquid droplets aresupplied to an outer peripheral portion of the discharge region D1.Therefore variation of particle diameter of the IPA liquid dropletstends to be significant and particles form readily at the outerperipheral portion of the discharge region D1. This is considered to bea factor for the double annular form of particles.

<Second Cleaning Test>

As the rotation speed of the substrate W increases, the IPA liquid filmin the IPA liquid droplet discharging step (S4 of FIG. 5) becomesthinner and the liquid droplets of the IPA jet begin to act directly onthe upper surface of the substrate W. Also as the rotation speed of thesubstrate W increases, gaps do no form in a locus of the dischargeregion D1 (see FIG. 6B) and the entirety of the substrate W begins to bescanned by the discharge region D1. Removal performance of the cleaningprocessing is thus improved as the rotation speed of the substrate Wincreases.

On the other hand, as the rotation speed of the substrate W becomeshigh, particles begin to form slightly at a central portion of the uppersurface of the substrate W (this state shall hereinafter referred to asthe “particle mode”). FIG. 9 is a schematic plan view for describing theparticle mode. When the rotation speed of the substrate W is high, acentrifugal force acts on the IPA supplied to the substrate W and theIPA moves toward the peripheral edge portion of the substrate W. Inparticular, the central portion of the upper surface of the substrate Wdries in some cases in a state where the discharge region D1 (see FIG.6B) is disposed at the peripheral edge portion of the substrate W. Itmay be considered that particles are formed slightly (the particle modebecame manifest) due to the drying of the central portion of thesubstrate W.

In the second cleaning test, the rotation speed of the substrate W inthe IPA liquid droplet discharging step (S4 of FIG. 5) of the examplewas varied at 300 rpm, 400 rpm, 500 rpm, and 1000 rpm. A degree ofcleanness of the front surface of the substrate W (removal performance(cleaning performance) of the cleaning processing) after the cleaningprocessing and whether or not the particle mode occurred on thesubstrate W after the cleaning processing were respectively observedvisually. Also, the number of particles of size not less than 26 (nm) onthe front surface of the substrate W after the cleaning processing wasalso measured.

The test results of the second cleaning test are shown in FIG. 10. FIG.10 shows, for the example, relationships of the rotation speed of thesubstrate W with respect to the occurrence of the particle mode afterthe cleaning processing and the removal performance of the cleaningprocessing. In regard to whether or not the particle mode occurred,“Good” is indicated in a case where the particle mode does not occur and“Insufficient” is indicated in a case where the particle mode occurs.Also, in regard to the degree of cleanness of the substrate W (removalperformance (cleaning performance) of the cleaning processing), “Good”is indicated in a case where the degree of cleanness is satisfactory and“Insufficient” is indicated in a case where the degree of cleanness ispoor. Also, the number of particles that formed at the central portionof the front surface of the substrate W after the cleaning processing isindicated in parenthesis.

It can be understood from FIG. 10 that the removal performance of thecleaning processing is low when the rotation speed of the substrate Winthe IPA liquid droplet discharging step (S4 of FIG. 5) is not more than300 rpm. As one cause, it is considered that the liquid film on thesubstrate W becomes too thick and consequently a sufficient amount ofIPA liquid droplets do not reach the upper surface of the substrate W inthe IPA liquid droplet discharging step (S4 of FIG. 5). Also, as anothercause, it is considered that the rotation speed of the substrate W istoo slow with respect to the moving speed of the discharge region D1,causing gaps to form in the locus of the discharge region D1 (see FIG.6B) so that, consequently, the entirety of the substrate W cannot bescanned by the discharge region D1.

It can be understood from FIG. 10 that the particle mode occurs when therotation speed of the substrate W in the IPA liquid droplet dischargingstep (S4) is not less than 500 rpm.

It can be understood from the above that the removal performance of thecleaning processing is high and the occurrence of the particle mode canbe suppressed when the rotation speed of the substrate W exceeds 300 rpmand is less than 500 rpm (and especially when the rotation speed isapproximately 400 rpm).

As described above, with the first preferred embodiment, IPA liquiddroplets are discharged from the double-fluid nozzle 16 toward thedischarge region D1 within the upper surface of the substrate W. Foreignmatter (particles, etc.) attached to the discharge region D1 are removedphysically by collision of the IPA liquid droplets against the uppersurface of the substrate W. The upper surface of the substrate W canthereby be cleaned satisfactorily.

Also, the IPA liquid film that covers the discharge region D1 within theupper surface of the substrate W is formed before the discharge of theIPA liquid droplets. Therefore, the IPA liquid droplets discharged fromthe double-fluid nozzle 16 collide against the IPA liquid film coveringthe discharge region D1. The IPA liquid droplets can thus be preventedfrom directly colliding against the upper surface of the substrate Winthe dry state at the start of IPA liquid droplet discharge at which theparticle diameter distribution of the IPA liquid droplets dischargedfrom the double-fluid nozzle 16 is unstable. Formation of particles inaccompaniment with the execution of the IPA liquid droplet dischargingstep (S4) can thus be suppressed.

By the above, the upper surface of the substrate W can be processedsatisfactorily using the IPA liquid droplets from a double-fluid nozzle16 while suppressing the formation of particles.

Also, damage of the substrate W in accompaniment with the supplying ofliquid droplets of the IPA jet can be suppressed to the minimum becausethe discharge region D1 within the upper surface of the substrate W isprotected by the IPA liquid film.

As described above, by setting the rotation speed of the substrate W to400 rpm and setting the discharge flow rate of IPA from the double-fluidnozzle 16 at a low value of 0.1 liters/minute, the thickness of the IPAliquid film on the upper surface of the substrate W can be kept thin.The particle performance of the cleaning processing using IPA canthereby be improved. Moreover, under these conditions, the formation ofparticles (the occurrence of the particle mode) in accompaniment withthe IPA liquid droplet discharging step (S4) can be suppressedeffectively.

Also, in the IPA liquid film forming step (S3), the IPA supplied to theupper surface of the substrate W is discharged from the double-fluidnozzle 16.

If, for instance, a liquid film forming nozzle (not shown) is providedseparately from the double-fluid nozzle 16 and the IPA to be supplied tothe upper surface of the substrate W is made to be discharged from theliquid film forming nozzle in the IPA liquid film forming step (S3), awaiting time until the start of IPA discharge from the double-fluidnozzle 16 (start of the IPA liquid droplet discharging step (S4)) arisesafter the end of execution of the IPA liquid film forming step (S3) dueto movement of the double-fluid nozzle 16 and the liquid film formingnozzle, etc., and the upper surface of the substrate W may dry duringthe waiting time.

On the other hand, with the first preferred embodiment, the IPA to besupplied to the upper surface of the substrate W is discharged from thedouble-fluid nozzle 16 in the IPA liquid film forming step (S3).Therefore, during the transition from the IPA liquid film forming step(S3) to the IPA liquid droplet discharging step (S4), the IPA can besupplied without interruption to the upper surface of the substrate W.Drying of the upper surface of the substrate W during the transitionfrom the IPA liquid film forming step (S3) to the IPA liquid dropletdischarging step (S4) can thus be suppressed. The formation of particlescan thus be suppressed effectively during the transition from the IPAliquid film forming step (S3) to the liquid droplet discharging step(S4).

Also, in the IPA post-supplying step (S5) performed after the IPA liquiddroplet discharging step (S4), a continuous stream of the IPA issupplied to the upper surface of the substrate W. The foreign matterremoved from the substrate W upper surface by the physical cleaning inthe IPA liquid droplet discharging step (S4) can thus be rinsed off bythe IPA and reattachment of the foreign matter onto the upper surface ofthe substrate W can thereby be suppressed or prevented.

Also, the rotation speed of the substrate W in the IPA post-supplyingstep (S5) is a higher speed (the second high rotation speed) than thatin the IPA liquid droplet discharging step (S4) and therefore a largecentrifugal force acts on the IPA supplied to the upper surface of thesubstrate W. The foreign matter removed from the upper surface of thesubstrate W by the physical cleaning can thereby be spun off from sidesof the substrate W together with the IPA and remaining of the foreignmatter on the upper surface of the substrate W can thus be suppressed orprevented.

Also, in the IPA post-supplying step (S5), the IPA supplied to the uppersurface of the substrate W is discharged from the double-fluid nozzle16.

If, for instance, a post-supplying nozzle (not shown) is providedseparately from the double-fluid nozzle 16 and the IPA to be supplied tothe upper surface of the substrate W is made to be discharged from thepost-supplying nozzle in the IPA post-supplying step (S5), a waitingtime until the start of IPA discharge from the post-supplying nozzle(start of the IPA post-supplying step (S5)) arises after the end ofexecution of the IPA liquid droplet discharging step (S4) due tomovement of the double-fluid nozzle 16 and the post-supplying nozzle,etc., and the upper surface of the substrate W may dry during thewaiting time.

On the other hand, with the first preferred embodiment, the IPA to besupplied to the upper surface of the substrate W is discharged from thedouble-fluid nozzle 16 in the IPA post-supplying step (S5). Therefore,during the transition from the IPA liquid droplet discharging step (S4)to the IPA post-supplying step (S5), the IPA can be supplied withoutinterruption to the upper surface of the substrate W, and drying of theupper surface of the substrate W during the transition from the IPAliquid droplet discharging step (S4) to the IPA post-supplying step (S5)can thus be suppressed effectively. Formation of particles during thetransition from the IPA liquid droplet discharging step (S4) to the IPApost-supplying step (S5) can thus be suppressed effectively.

Also, in the IPA liquid droplet discharging step (S4), in which theupper surface of the substrate W is physically cleaned by the IPA liquiddroplets, the IPA expelled from the substrate W contains the foreignmatter removed from the substrate W. During the IPA liquid dropdischarging step (S4), the first guard 38 faces the peripheral endsurface of the substrate W and the IPA that contains the foreign matterbecomes attached to the first guard 38.

In the drying step (S7) according to the first preferred embodiment, thesecond guard 39 is made to face the peripheral end surface of thesubstrate W instead of the first guard 38 that has theforeign-matter-containing IPA attached thereto. Therefore during thedrying step (S7), the substrate W after the cleaning processing can besuppressed effectively from being contaminated by the IPA attached tothe guard facing the peripheral end surface of the substrate W. Thesubstrate W can thereby be processed satisfactorily using the IPA liquiddroplets from the double-fluid nozzle 16 while suppressing the formationof particles even more effectively.

FIG. 11 is an illustrative diagram of a portion of a substrateprocessing apparatus 101 which executes a substrate processing methodaccording to a second preferred embodiment of the present invention.FIGS. 12A and 12B are illustrative diagrams for describing the IPAliquid droplet discharging step (S4) in a cleaning processing accordingto the second preferred embodiment of the present invention.

In FIG. 11 and FIGS. 12A and 12B, portions corresponding to respectiveportions indicated in the first preferred embodiment shall be indicatedby attaching the same reference symbols as in the case of FIG. 1 to FIG.10 and description thereof shall be omitted.

The substrate processing apparatus 101 according to the second preferredembodiment differs from the substrate processing apparatus 1 accordingto the first preferred embodiment in the point of being provided with anadditional organic solvent supplying unit (fourth organic solventsupplying unit) 102 in addition to the organic solvent supplying unit 4.

The additional organic solvent supplying unit 102 includes an organicsolvent nozzle 103 constituted of a straight nozzle. The organic solventnozzle 103 is a nozzle that discharges IPA in a continuous stream modeand is mounted on the nozzle arm 17. Therefore, when the nozzle arm 17is swung to move the position of the discharge region D1 (see FIGS. 12Aand 12B), the double-fluid nozzle 16 and the organic solvent nozzle 103move while keeping fixed a positional relationship of the double-fluidnozzle 16 and the organic solvent nozzle 103. The organic solvent nozzle103 is mounted on the nozzle arm 17 so that an IPA supply region Su10 inthe upper surface of the substrate W is positioned at an outer side in aradial direction with respect to the discharge region D1.

The additional organic solvent supplying unit 102 includes an additionalorganic solvent piping 104 guiding IPA from an IPA supply source to theorganic solvent nozzle 103 and an additional organic solvent valve 105opening and closing the additional organic solvent piping 104. When theadditional organic solvent valve 105 is opened, liquid IPA at ordinarytemperature from the IPA supply source is supplied to the organicsolvent nozzle 103 through the additional organic solvent piping 104. Acontinuous stream of the IPA is thereby discharged from the organicsolvent nozzle 103.

As shown indicated by the two-dot-and-dash line in FIG. 2B, in additionto the description of the controller 7 in the first embodiment, thecontroller 7 further is connected to the operations of the additionalorganic solvent valve 105, and the like. The controller 7 controls theopening and closing operation etc. on the additional organic solventvalve 105, etc., in accordance with a predetermined program.

In the cleaning processing according to the second preferred embodiment,a cleaning processing equivalent to the cleaning processing according tothe first preferred embodiment (the cleaning processing shown in FIG. 5)is executed. In the IPA liquid droplet discharging step (S4), dischargeof the continuous stream of IPA from the organic solvent nozzle 103 isperformed in parallel to the discharge of IPA liquid droplets from thedouble-fluid nozzle 16. The step differs from the IPA liquid dropletdischarging step (S4) according to the first preferred embodiment inthis point. The point of difference shall now be described.

In the IPA liquid droplet discharging step (S4), the controller 7controls the arm swinging unit 19 to make the double-fluid nozzle 16,which is discharging the jet of IPA liquid droplets, move back and forthhorizontally between the central position and the peripheral edgeposition, and the position of the discharge region D1 is thereby movedbetween the central portion of the substrate Wand the peripheral edgeportion of the substrate W (discharge region moving step). The organicsolvent nozzle 103 is also moved back and forth horizontallyaccordingly.

When as shown in FIG. 12A, the double-fluid nozzle 16 is being movedfrom the peripheral edge position toward the central position, thecontroller 7 opens the additional organic solvent valve 105 to make acontinuous stream of IPA be discharged from the organic solvent nozzle103 (additional organic solvent supplying step). The continuous streamof IPA is thereby supplied to a rearward position with respect to adirection of progress of the discharge region D1 in the upper surface ofthe substrate W. On the other hand, when as shown in FIG. 12B, thedouble-fluid nozzle 16 is being moved from the central position towardthe peripheral edge position, the controller 7 closes the additionalorganic solvent valve 105 so that the IPA is not discharged from theorganic solvent nozzle 103.

In other words, the continuous stream of IPA is discharged from theorganic solvent nozzle 103 when the supply region Su1 is positionedrearward with respect to the direction of progress of the dischargeregion D1, and the IPA is not discharged from the organic solvent nozzle103 when the IPA supply region Su1 is positioned forward with respect tothe direction of progress of the discharge region D1.

With the second preferred embodiment, regardless of where in the uppersurface of the substrate W the position of the discharge region D1 isdisposed, the IPA is supplied separately to a vicinity of the positionof the discharge region D1. If the upper surface of the substrate Wdries during the IPA liquid droplet discharging step (S4), particles mayform in the dried region. However, the IPA is supplied to the vicinityof the position of the discharge region D1 and therefore drying of theupper surface of the substrate W during the IPA liquid dropletdischarging step (S4) can be prevented.

If, for instance, the IPA supply region Su1 is disposed at a forwardposition with respect to the direction of progress of the dischargeregion D1, the IPA liquid film at the discharge region D1 becomes thick.If the liquid film that covers the discharge region D1 is thick, the IPAmay splash in accompaniment with the discharge of the IPA liquiddroplets onto the discharge region. Contaminants contained in the IPAmay scatter to the periphery due to the splashing of the IPA and maycause particle formation.

With the second preferred embodiment, the IPA is supplied only to therearward position with respect to the direction of progress of thedischarge region D1 and therefore the IPA liquid film at the dischargeregion D1 can be kept thin while preventing the drying of the uppersurface of the substrate W. Splashing of the IPA discharged onto thedischarge region D1 can thus be suppressed. Formation of particles inaccompaniment with the execution of the IPA liquid droplet dischargingstep (S4) can thereby be suppressed more effectively.

Although two preferred embodiments of the present invention have beendescribed above, the present invention may be implemented in yet othermodes.

For example, in the second preferred embodiment, the organic solventnozzle 103 may be mounted on the nozzle arm 17 so that the IPA supplyregion Su1 in the upper surface of the substrate W is positioned at aninner side in the radial direction with respect to the discharge regionD1. In this case, the continuous stream of IPA is discharged from theorganic solvent nozzle 103 when the double-fluid nozzle 16 is moved fromthe central position toward the peripheral edge position. On the otherhand, the IPA is not discharged from the organic solvent nozzle 103 whenthe double-fluid nozzle 16 is moved from the peripheral edge positiontoward the central position. In other words, the continuous stream ofIPA is discharged from the organic solvent nozzle 103 when the supplyregion Su1 is positioned rearward with respect to the direction ofprogress of the discharge region D1, and the IPA is not discharged fromthe organic solvent nozzle 103 when the IPA supply region Su1 ispositioned forward with respect to the direction of progress of thedischarge region D1. In this case, actions and effects equivalent tothose of the second preferred embodiment are exhibited.

Also, with each of the first and second preferred embodiments, thesubstrate W having the SiO₂ 63 disposed at the front surface of thesilicon substrate 61 (see FIG. 3) was subject to processing. In place ofthe substrate W, a substrate W1, described below, may be subject to theprocessing by the substrate processing apparatus 1 or 101.

FIG. 13 is an enlarged sectional view of a vicinity of a front surfaceof the substrate W1 to be processed by the substrate processingapparatus 1 or 101.

The substrate W1 to be processed constitutes a base of a semiconductordevice having a multilayer wiring structure of copper wirings and has aninsulating film 71, constituted of a low-k (a low dielectric constantmaterial of lower relative dielectric constant than SiO₂, morepreferably an ULK (ultra low-k)) film formed at a surface layer portion.The insulating film 71 functions as an insulating layer. Wiring trenches72 are formed in the insulating film 71 by digging from its frontsurface. A plurality of the wiring trenches 72 are formed at fixedintervals in a right/left direction in FIG. 13 with each extending in adirection orthogonal to a paper surface of FIG. 13. A copper wiring 73is embedded in each wiring trench 72. A front surface of the copperwiring 73 is made substantially flush with the front surface of theinsulating film 71.

FIGS. 14A to 14C are illustrative sectional views showing a method formanufacturing the substrate W1 in order of process.

First, the insulating film 71 is formed on a semiconductor substrate bya CVD method. Thereafter, the wiring trenches 72 are formed by reactiveion etching in the surface layer portion of the insulating film 71 asshown in FIG. 14A. Thereafter, a copper film 74 is formed on an uppersurface of the insulating film 71 and inside each wiring trench 72 asshown in FIG. 14B. As shown in FIG. 14B, the copper film 74 fills theinteriors of the wiring trenches 72 completely and is also formed on theinsulating film 71 outside the wiring trenches 72.

Next, portions of the copper film 74 protruding outside the respectivewiring trenches are removed selectively by a CMP method. A front surfaceof the copper film 74 is thereby made a flat surface that issubstantially flush with the front surface of the insulating film 71 andthe copper wirings 73 are formed as shown in FIG. 14C (secondpreliminary preparation step).

The copper wirings 73 are formed by polishing the copper film 74 by theCMP method and therefore copper polishing scraps (slurry) 75 are presenton the surface layer portion of the substrate W1 immediately aftermanufacture. The substrate processing apparatus 1 applies the cleaningprocessing to the substrate W1 to remove the copper polishing scraps 75from the substrate W1.

Generally in such a cleaning processing, a chemical liquid, such ashydrofluoric acid (HF), SC2 (hydrochloric acid/hydrogen peroxidemixture), SPM (sulfuric acid/hydrogen peroxide mixture), etc., issupplied to a substrate held by a spin chuck and thereafter, water, suchas pure water (de-ionized water), etc., is supplied to rinse off thechemical liquid on the substrate with the pure water (rinsingprocessing).

However, if pure water is supplied to the front surface of the substrateW1 during the rinsing processing, the front surfaces of the copperwirings 73 may become oxidized and this may influence the performance ofthe semiconductor device after manufacture. Thus with the substrateprocessing apparatus 1, IPA (organic solvent) is used as a cleaningliquid to clean the front surface (upper surface) of the substrate W1.IPA (organic solvent) is low in oxidizing power with respect to copper.The front surface (upper surface) of the substrate W1 can thus becleaned satisfactorily without excessively etching the front surfaces ofthe copper wirings 73.

Also, the front surface of the insulating film 71 exhibits highhydrophobicity (lyophobicity) because a low-k material has a highcontact angle. However, the front surface of the insulating film 71having high hydrophobicity can be wetted satisfactorily by using IPA orother organic solvent, having a low surface tension, as the cleaningliquid. An IPA liquid film that covers an entirety of the upper surfaceof the substrate W1 can thereby be formed satisfactorily.

In this case, if the front surface of the substrate W1 exhibitshydrophobicity, the IPA tends to dry non-uniformly on the upper surface(front surface) of the substrate W1 in the drying step (S7). There isthus a problem that particles tend to form on the upper surface of thesubstrate W1 during the drying step (S7). However, in the presentpreferred embodiment, the drying of the substrate W1 is performed in astate where the upper surface of the substrate W1 is covered by theannular gas streams from the gas discharge nozzle 6 and therefore theformation of particles on the upper surface of the substrate W1 can besuppressed.

Also in each of the first and second preferred embodiments, a liquidfilm forming nozzle (not shown), constituted of a straight nozzlecapable of discharging a continuous stream, may be provided separatelyfrom the double-fluid nozzle 16 and the IPA to be supplied to the uppersurface of the substrate Win the IPA liquid film forming step (S3) maybe discharged from the liquid film forming nozzle. In this case, asecond organic solvent supplying unit includes the liquid film formingnozzle and an IPA supplying apparatus supplying the IPA to the liquidfilm forming nozzle.

Also in each of the first and second preferred embodiments, apost-supplying nozzle (not shown), constituted of a straight nozzlecapable of discharging a continuous stream, maybe provided separatelyfrom the double-fluid nozzle 16 and the IPA to be supplied to the uppersurface of the substrate W in the IPA post-supplying step (S5) may bedischarged from the post-supplying nozzle. In this case, a third organicsolvent supplying unit includes the post-supplying nozzle and an IPAsupplying apparatus supplying the IPA to the post-supplying nozzle.

In this case, the IPA supplying apparatus for the liquid film formingnozzle and the IPA supplying apparatus for the post-supplying nozzlemaybe an apparatus in common or may be separate, individual apparatuses.Further, a single nozzle may be used in common as the liquid filmforming nozzle (not shown) and the post-supplying nozzle (not shown).

Also, although with each of the first and second preferred embodiments,it was described that the rotation speed of the substrate W in the IPApost-supplying step (S5) is a higher speed than the rotation speed ofthe substrate Win the IPA liquid droplet discharging step (S4), it mayinstead be approximately the same speed as the rotation speed of thesubstrate W in the IPA liquid droplet discharging step or may be a lowerspeed than the rotation speed of the substrate W in that step.

Also, the IPA post-supplying step (S5) may be abolished. That is, thedrying step (S7) may be entered immediately after the end of the IPAliquid droplet discharging step (S4). In this case, the foreign matterremoved in the IPA liquid droplet discharging step (S4) is preferablyeliminated from above the substrate W by supplying a gas after the endof the IPA liquid droplet discharging step (S4).

Also, although in each of the first and second preferred embodiments,the changing of the guard facing the peripheral end surface of thesubstrate W (S6) is executed after the end of the IPA post-supplyingstep (S5) and before starting the drying step (S7), it may be performedbefore the end of the IPA post-supplying step (S5). For example, it maybe performed before the start of IPA post-supplying step (S5) after theend of the IPA liquid droplet discharging step.

Also, the second guard 39 may be made to face the peripheral end surfaceof the substrate W during the drying step (S7) without performing thechanging of the guard facing the peripheral end surface of the substrateW (S6).

Also, although it was described that the gas discharge nozzle 6 has thethree gas discharge ports 44, 45, and 46, it does not have to have allthree gas discharge ports 44, 45, and 46 and suffices to have at leastone gas discharge port.

Also, in the first preferred embodiment, just one of either thesubstrate W or the double-fluid nozzle 16 may be moved to make the IPAliquid droplets collide against the entirety of the upper surface of thesubstrate W. Specifically, the double-fluid nozzle 16 may be moved in astate where the substrate W is set still so that the discharge region D1passes across the entirety of the upper surface of the substrate W.Also, the substrate W may be moved in a state where the double-fluidnozzle 16 is set still so that the discharge region D1 passes across theentirety of the upper surface of the substrate W.

Also in each of the first and second preferred embodiments, the movementlocus of the discharge region D1 on the upper surface of the substrate Wmay be a straight line. That is, the locus may be a straight lineextending along the upper surface of the substrate W held by the spinchuck 3 and passing through a central portion (preferably a center) ofthe upper surface of the substrate W when viewed from a perpendiculardirection perpendicular to the upper surface of the substrate W.

Also, although with each of the first and second preferred embodiments,it was described that the discharge region D1 is arranged to be movedback and forth (half-scanned) between one peripheral edge portion of theupper surface of the substrate W and the upper surface central portionof the substrate W, it may instead be arranged to be moved(full-scanned) between one peripheral edge portion of the upper surfaceof the substrate W and another peripheral edge portion at an oppositeside of the one peripheral edge portion across the substrate W uppersurface central portion.

Further, the gas discharge nozzle 6 may be abolished.

Also, although with each of the first and second preferred embodiments,the two stage type processing cup 5 was described as an example, thepresent invention is applicable to a substrate processing apparatusincluding a processing cup of a multiple stage type or a single cuptype.

Also, although with each of the first and second preferred embodiments,the externally-mixing type double-fluid nozzle 16, which forms liquiddroplets by mixing a gas and a liquid by making these collide outsidethe nozzle body (at the outer cylinder 26 (see FIG. 6)), was describedas an example of the double-fluid nozzle 16, the present invention isalso applicable to an internally-mixing type double-fluid nozzle, whichforms liquid droplets by mixing a gas and a liquid inside the nozzlebody.

Also, the organic solvent used in the present invention is notrestricted to IPA. The organic solvent includes at least one of IPA,methanol, ethanol, HFE (hydrofluoroether), acetone, andtrans-1,2-dichloroethylene. Also, the organic solvent is not restrictedto a case of being constituted of a single component but may also be aliquid mixed with another component. For example, it may be a mixedliquid of IPA and acetone or a mixed liquid of IPA and methanol.

Also, although with each of the first and second preferred embodiments,the case where the substrate processing apparatus 1 or 101 is anapparatus arranged to process a disk-shaped substrate was described, thesubstrate processing apparatus 1 or 101 may instead be an apparatusarranged to process a polygonal substrate, such as a substrate forliquid crystal display device, etc.

While preferred embodiments of the present invention have been describedin detail above, these are merely specific examples used to clarify thetechnical contents of the present invention, and the present inventionshould not be interpreted as being limited only to these specificexamples, and the spirit and scope of the present invention shall belimited only by the appended claims.

The present application corresponds to Japanese Patent Application No.2014-265537 filed on Dec. 26, 2014 in the Japan Patent Office, and theentire disclosure of this application is incorporated herein byreference.

What is claimed is:
 1. A substrate processing method comprising: asubstrate holding step of holding a substrate horizontally; a liquiddroplet discharging step wherein liquid droplets of an organic solvent,the liquid droplets being formed by mixing the organic solvent and agas, are discharged from a double-fluid nozzle toward a predetermineddischarge region within an upper surface of the substrate, while a firstguard faces a peripheral end surface of the substrate; a liquid filmforming step, executed before the liquid droplet discharging step, ofsupplying the organic solvent onto the upper surface of the substrate toform a liquid film of the organic solvent covering the discharge regionon the upper surface of the substrate; a drying step of rotating thesubstrate around the rotational axis, without supplying the organicsolvent to the upper surface of the substrate, to dry the upper surfaceof the substrate; and a facing guard changing step of changing the guardfacing the peripheral end surface of the substrate from the first guardto a second guard, differing from the first guard, after the liquiddroplet discharging step is ended and before the drying step isexecuted.
 2. The substrate processing method according to claim 1,further comprising: a first rotating step of rotating the substratearound the rotational axis in parallel with the liquid dropletdischarging step.
 3. The substrate processing method according to claim2, further comprising: a post-supplying step of supplying the organicsolvent to the upper surface of the substrate after the liquid dropletdischarging step.
 4. The substrate processing method according to claim3, further comprising: a second rotating step, executed in parallel withthe post-supplying step, of rotating the substrate around the rotationalaxis at a higher speed than that in the first rotating step.
 5. Thesubstrate processing method according to claim 3, wherein in thepost-supplying step, the organic solvent is supplied to the double-fluidnozzle without supplying the gas, so as to discharge the organic solventin a continuous stream mode from the double-fluid nozzle.
 6. Thesubstrate treatment method according to claim 1, further comprising anozzle moving step of moving the double fluid nozzle; wherein the liquiddroplet discharging step starts discharging of droplets of the organicsolvent to a discharge region of the organic solvent on the uppersurface of the substrate at the end of the liquid film forming step. 7.The treatment method according to claim 6, wherein the discharge regionincludes a peripheral edge on the upper surface of the substrate; andthe liquid droplet discharging step starts discharging of droplets ofthe organic solvent to the peripheral edge on the upper surface of thesubstrate.
 8. The substrate processing method according to claim 1,further comprising: a first preliminary preparation step of preparing asilicon substrate, having SiO2 disposed at the upper surface, as thesubstrate.
 9. The substrate processing method according to claim 1,further comprising: a second preliminary preparation step of preparing asemiconductor substrate, including an insulating film constituted of alow dielectric constant material of lower relative dielectric constantthan SiO2 and a copper wiring disposed on the insulating film, as thesubstrate.
 10. A substrate processing method comprising: a substrateholding step of holding a substrate horizontally; a liquid dropletdischarging step wherein liquid droplets of an organic solvent, theliquid droplets being formed by mixing the organic solvent and a gas,are discharged from a double-fluid nozzle toward a predetermineddischarge region within an upper surface of the substrate; a liquid filmforming step, executed before the liquid droplet discharging step, ofsupplying the organic solvent onto the upper surface of the substrate toform a liquid film of the organic solvent covering the discharge regionon the upper surface of the substrate; a discharge region moving step ofmoving the position of the discharge region within the upper surface ofthe substrate; and an additional organic solvent supplying step ofsupplying, in parallel to the discharge region moving step, the organicsolvent to a rearward position with respect to a direction of progressof the discharge region; and wherein the organic solvent is not suppliedto a forward position with respect to the direction of progress of thedischarge region in the additional organic solvent supplying step. 11.The substrate processing method according to claim 10, furthercomprising: a first rotating step of rotating the substrate around therotational axis in parallel with the liquid droplet discharging step.12. The substrate processing method according to claim 11, furthercomprising: a post-supplying step of supplying the organic solvent tothe upper surface of the substrate after the liquid droplet dischargingstep.
 13. The substrate processing method according to claim 12, furthercomprising: a second rotating step, executed in parallel with thepost-supplying step, of rotating the substrate around the rotationalaxis at a higher speed than that in the first rotating step.
 14. Thesubstrate processing method according to claim 12, wherein in thepost-supplying step, the organic solvent is supplied to the double-fluidnozzle without supplying the gas, so as to discharge the organic solventin a continuous stream mode from the double-fluid nozzle.
 15. Thesubstrate treatment method according to claim 10, further comprising anozzle moving step of moving the double fluid nozzle; wherein the liquiddroplet discharging step starts discharging of droplets of the organicsolvent to a discharge region of the organic solvent on the uppersurface of the substrate at the end of the liquid film forming step. 16.The treatment method according to claim 15, wherein the discharge regionincludes a peripheral edge on the upper surface of the substrate; andthe liquid droplet discharging step starts discharging of droplets ofthe organic solvent to the peripheral edge on the upper surface of thesubstrate.
 17. The substrate processing method according to claim 10,further comprising: a first preliminary preparation step of preparing asilicon substrate, having SiO2 disposed at the upper surface, as thesubstrate.
 18. The substrate processing method according to claim 10,further comprising: a second preliminary preparation step of preparing asemiconductor substrate, including an insulating film constituted of alow dielectric constant material of lower relative dielectric constantthan SiO2 and a copper wiring disposed on the insulating film, as thesubstrate.